Ujihara Masaki, Mitamura Koji, Torikai Naoya, Imae Toyoko
Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
Langmuir. 2006 Apr 11;22(8):3656-61. doi: 10.1021/la053202n.
A newly designed 1.5th generation poly(amido amine) dendrimer with an azacrown core, hexylene spacers, and octyl terminals was spread on gold nanoparticle (Au-NP) suspension. The surface pressure-area isothermal curves indicated that the molecular area of dendrimer on Au-NP suspension was significantly smaller than that on water, indicating the formation of dendrimer/Au-NP composites. The dendrimer Langmuir films on the Au-NP suspension were transferred to copper grids at various surface pressures and observed by transmission electron microscopy. The transferred films consisted of a fractal-like network of nanoparticles at low surface pressure and of a defect-rich monolayer of nanoparticles at high surface pressure. From these results, it was suggested that the dendrimers bind Au-NPs, and dendrimer/Au-NP composites formed networks or monolayers at the interface. From the intensity decrease of the Au plasmon band of Au-NP suspension after the formation of composite, it was estimated that some (approximately 14) dendrimer molecules bind to one Au-NP. Furthermore, neutron reflectivity at the air/suspension interface and X-ray reflectivity of the film transferred on a silicon substrate revealed that the dendrimer molecules are localized on the upper-half surface of Au-NP. Metal affinity of azacrown, flexibility of hexylene spacer, and amphiphilicity of dendrimer with octyl terminals played important roles for the formation of dendrimer/Au-NP hybrid films. The present investigation proposed a new method to fabricate the self-assembled functional polymer/nanoparticle hybrid film.
一种新设计的具有氮杂冠醚核心、己撑间隔基和辛基末端的1.5代聚(酰胺胺)树枝状大分子被铺展在金纳米颗粒(Au-NP)悬浮液上。表面压力-面积等温线表明,树枝状大分子在Au-NP悬浮液上的分子面积明显小于在水上的分子面积,这表明形成了树枝状大分子/Au-NP复合材料。将Au-NP悬浮液上的树枝状大分子朗缪尔膜在不同表面压力下转移到铜网上,并用透射电子显微镜观察。转移后的膜在低表面压力下由类似分形网络的纳米颗粒组成,在高表面压力下由富含缺陷的纳米颗粒单层组成。从这些结果可以推测,树枝状大分子与Au-NP结合,并且树枝状大分子/Au-NP复合材料在界面处形成网络或单层。根据复合材料形成后Au-NP悬浮液的Au等离子体带强度降低,估计约有14个树枝状大分子分子与一个Au-NP结合。此外,空气/悬浮液界面处的中子反射率和转移到硅衬底上的膜的X射线反射率表明,树枝状大分子分子位于Au-NP的上半表面。氮杂冠醚的金属亲和力、己撑间隔基的柔韧性以及具有辛基末端的树枝状大分子的两亲性对树枝状大分子/Au-NP混合膜的形成起到了重要作用。本研究提出了一种制备自组装功能聚合物/纳米颗粒混合膜的新方法。